Process for breaking petroleum emulsions employing certain oxyalkylated sucroses



Jan. 7, 1958 M. DE GROOTE EiAL 2,819,215

PROCESS FOR BREAKING PETROLEUM EMULSIONS EMPLOYING CERTAIN QXYALKYLATED SUCROSES Filed May 24, 1954 FIG. 2 l0 SUCROSE CaHeO [00 A B INVENTORS CaHeO C4He0 2,819,215 Patented Jan. 7, 1958 PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPLOYING CERTAIN OXYALKYLATED SUCROSES Melvin De Groote, University City, and Owen H. Pettingill, Kirkwood, Mm, assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware Application May 24, 1954, Serial No. 431,782

20 Claims. (Cl. 252-331) This invention is a continuation-in-part of our copending application, Serial No. 417,566, filed March 22, 1954, now abandoned.

This invention relates to processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities particularly inorganic salts, from pipeline oil.

More specifically then the present invention is concerned with a process for breaking petroleum emulsions employing a demulsifier including a cogeneric mixture of homologous series of glycol ethers of sucrose. The cogeneric mixtures are derived exclusively'from sucrose, ethylene oxide, propylene oxide and butylene oxide, in such weight proportions so the average composition of said cogeneric mixture in terms of the initial reactants lies approximately within the truncated triangular pyramid identified as E, H, F, I and G, J, in Figurel; with the proviso that the percentage of ethylene oxide, by weight, is within the limits of 2% to 39.5% and the remaining three initial reactants recalculated to 100% basis lie approximately within the triangular area defined in Figure 2 by points 1, 4, 6. However, as will be pointed out subsequently the same ultimate compositions may be employed using anyoneof the three oxides last.

The oxyalkylation of sucrose by means of ethylene oxide, propylene oxide, or butylene oxide hasbeen described in the literature. One can use instead of the oxides the corresponding alkylene carbonates, to wit, ethylene carbonate, propylene carbonate, or ,butylene carbonate.

As is well known, the oxyalkylation derivatives from any oxyalkylation-susceptible compound, are prepared by the addition reaction between such oxides and such compound. The addition reaction is advantageously carried out at an elevated temperature and pressure and in the presence of a small amount of alkaline catalyst. Usually, the catalyst is sodium hydroxide or sodium methylate. The reaction temperature is apt to be 140 C. or somewhat less, and the reaction pressure not in excess of 30 to 50 pounds per square inch.

Asto further information in regard to .the mechanical steps involved in oxyalkylation, see U. S. Patent No.

2 2,499,365, dated March .7, 1950, to DeGroote et a]. Particular reference is made to columns .92 et seq.

The oxyalkylation of a liquid or a solid which can be melted at comparatively low temperature (under C.) without decomposition or is soluble in an inert solvent, such as xylene, presents little or no mechanical difiiculties in the oxyalkylation .step. When one .has a solid which cannot be melted, or decomposes on melting, and is insoluble in xylene, a slurry maybe employed asinthe case of. the oxyalkylation'of sucrose. See U.. S. Patent No. 2,652,394, dated .September 15, 1953,10 De Groote.

The oxyalkylation of sucrose can be accomplished in a number of ways and the particular procedure em-, ployed is immaterial. .Specific reference is made to the instant application which is concerned with ethylene oxide, and butylene oxide, or the equivalents. Actually, whether one uses ethylene oxide or butylene oxide or, for that matter, propylene oxide, one preferably starts with'either the powdered sucrose suspended as a slurry in xylene or a similarinactive. solvent; or one employs an alkylene carbonate such as ethylene carbonate, butylene carbonate, or propylene carbonate, for the initial oxyalkylation. When such initial oxyalkylation has gone far enoughto :convert the solid mass into a product which is at least liquid at oxyalkylation temperature it can beisubjected to'the oxides as differentiated from the carbonates. The carbonates, ofcourse, cost more, than the oxides.

When butylene oxide isused the same procedurezcan befollowed as in the use of propylene oxide or ethylene ox-ideasdescribed-in aforementioned U. "S. Patent No. 2,652,394 dated September 15, 1953, to De Groote. Indeed, the oxyalkylation of sucrose is substantiallycomparable to the oxyalkylation of sorbitol particularly if one uses powdered sorbitol in the-formof .a slurry. Such slurry is the equivalent of a slurry of powdered sucrose.

Referring momentarily to oxyalkylation of sucrose, various suitable proceduresare well known. In the case of butylene oxide the same procedure can be employed as in the use of propylene oxide in the oxypropylation of sorbitol as described in U. S. Patent No. 2,552,528, dated May 15, 1951, to De Groote. Although this patentdescribes the use of molten sorbitol one'cansubstitute a slurry of solid'sorbitol, or for that matter a slurry of solid sucrose, and proceed in identically the same manner. Indeed, we have used identically the same procedure starting with finely powdered sucrose as a slurry inabout one-half its weight of xylene. Instead of using 1600 grams of propylene oxidethere-was used instead 1800 grams of butylene ;0X d e (mixed straight chain isomers).

I-nExample B, instead of using 1100 gramsof the propyle-ne oxide derived intermediate from ExampleA, preceding, there was used instead ll91 grams of the hutylene oxide derived intermediate, Example A. Instead of using 1327 grams of propyleneoxide therewas added 1493 gra-Insof butylene oxide.

jIn Ex mple C, instead of using 1 1.49gramsof-propylene oxide derived intermediate Example B, fro rn the preceding example, there was used instead l27l grams of butyleneoxide derived intermediate B. Instead of adding 1995 grams of propylene oxide in this ,stage, there was added instead 2345 grams of butylene oxide.

In Example D, instead of 743 grams of the propylene oxide derived intermediate from Example C, preceding,

there was-used 831 grams of the butylene oxide derived intermediate. Instead of adding 637 grams of propylene oxide in this stage, there was added 71-7 grams of butylene I oxide.

It will be noted at this stage the ratio of butylene oxide to sucrose was approximately 100-to-1, and the amount of sucrose represents less than 3%, by weight, of the end product and the amount of butylene oxide represented over 97%.

Example E was conducted in the same manner except that the initial reactant was Example D, preceding, and instead of using 566 grams there was used instead 628 grams of the reactant. Instead of adding 563 grams of propylene oxide, there was added instead 633 grams of butylene oxide.

In this last example, five grams of sodium methylate were added as a catalyst to speed up the final stage .of reaction. Operating conditions, such as temperature, time factor, etc., were substantially the same .as described in the corresponding Examples A, B, D, C, and E, in aforementioned U. S. Patent 2,552,528.

It will be noted that in this final product approximately 200 moles of butylene oxide were exployed per mole of sucrose. On a percentage basis, the products represented approximately 1% sucrose and 99% butylene oxide. 1

All examples, except the first stage, were substantially water-insoluble and xylene soluble;

It is immaterial in what order the oxides are added to sucrose so as to obtain the herein described products. However, our preference is to add butylene oxide first, then propylene oxide and then ethylene oxide. There are two advantages in so doing. The first advantage is that products obtained as far as the general average goes following this succession of oxides appears to give the most valuable product. Secondly, it is easier from a purely manipulative standpoint to oxybutylate molten sucrose than to oxyethylate. There is less pressure on the autoclave than in oxyethylate. There is less pressure on the autoclave than in oxyethylation. However, oxyethylation can be conducted perfectly satisfactorily.

So far as the use of butylene oxide is concerned we prefer to use the straight chain isomers.

CHzCHCHz-CH:

CHa-CHCHOH:

or a mixture of the two.

As noted previously, one can oxyethylate first and then add either one of the other two oxides, to wit, butylene oxide or propylene oxide. Similarly, one can add either oxide first, that is, propylene oxide or butylene oxide, and then add ethylene oxide, followed by the addition of the other oxide. Also, as is obvious, one need not add all the ethylene oxide alone or all the butylene'oxide alone or all the propylene oxide alone. One could make a mixture of either one of the two, or all three, and use such mixture or mixtures as an oxyalkylating agent. Furthermore, one can add a fraction of any particular oxide and then add the rest at a subsequent stage. This may be applied not only to a single oxide but also to two of the three, or all three, of the oxides employed.

For the purpose of resolving petroleum emulsions of the water-inoil type, we prefer to employ oxyalkylated derivatives, which are obtained by the use of monoepoxides, in such manner that the derivatives so obtained have sufiicient hydrophile character to meet at least the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent such test for emulsification using a water-insoluble solvent;

generally xylene, is described as an index of surface activity.

The above mentioned test, i. e., a conventional emulsification test simply means that the preferred product for demulsification is soluble in a solvent having hydrophobe properties or in an oxygenated water-insolublesolvent, or a mixture containing a fraction of such solvent with the proviso that when such solution in a hydro carbon solvent is shaken with water the product may remain in the nonaqueous solvent or, for that matter, it may pass into the aqueous solvent. In other words, although it is xylene soluble, for example, it may also be water soluble to an equal or greater degree.

For purpose of convenience what is said hereinafter will be divided into four parts:

Part 1 is concerned with the oxyalkylation of sucrose broadly so as to obtain products within the compositional limits of the herein described invention;

Part 2 is concerned with binary or tertiary products derived from sucrose and a single oxide, or sucrose and two oxides, which may be looked upon as intermediate products. More conveniently, the binary compositions may be considered as sub-intermediates and the tertiary compositional products as intermediates, all of which will be plain in light of the subsequent specification. Such intermediates are reacted with one more component, for instance, ethylene oxide, to give the four-component product described in Part 1, preceding.

Part 3 is concerned essentially with the oxyalkylation of the intermediate described in Part 2, preceding. Needless to say, if the intermediate were obtained by the use of butylene oxide and ethylene oxide it would be subjected to oxypropylation; if obtained from butylene oxide and propylene oxide it would be subjected to oxyethylation; and if obtained from propylene oxide 'and ethylene oxide it would be subjected to oxybutylation.

Part 4 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds.

PART 1 The present invention is concerned with a cogeneric mixture which is the end product of a reaction or reactions involving 4 reactants. Assuming completeness of reaction and based on a mathematical average, the final product is characterized most conveniently in terms of the 4 component reactants. This phase of the invention is described elsewhere in greater detail.

In representing a mixture or an end product derived from 2 components or 3 components, there is no difliculty as far as using the plane surface of an ordinary printed sheet. For example, a 3-component system is usually represented by a triangle in which the apexes represent .of each component and any mixture or reaction product in terms of the 3 components is represented by a point in the triangular area in which the composition is indicated by perpendiculars from such point to the sides.

Chemists and physicists ordinarily characterize a 4- component system by using a solid, i. e., a regular tetrahedron. In this particular presentation each point or apex represents 100% of each of the 4 components, each of the 6 edges represents a line or binary mixture of the 2 components represented by the apexes or points at the end of the line or edge. Each of the 4 triangles or faces represent a tertiary mixture of the 3 components represented by the 3 corners or apexes and obviously signify the complete absence of the 4th component indicated by the corner or apex opposite the triangular face.

However, as soon as one moves to a point within the regular tetrahedron one has definitely characterized and specified a 4-component mixture in which the 4 components add up to 100%. Such a representation of a 4- component system is described in detail in U. S. Patent 2,549,438 to De Groote et al.

The invention will be described by reference to the accompanying drawings, which illustrate, in conventional graphical form, compositions used in accordance with the invention in terms of the four components. In the drawings, Figure 1 is a conventional tetrahedron in which a trapezoidal area is blocked out and which defines the scope of the invention. Figure 2 is a planar figure by' which, having a fixed amount oi one. constituent, .theother three .may be determined.

Referring now toFigure' l,.'the composition represented by the block which is really a truncated triangular pyramid is designated by E, H; RI; and G, J. Bear in mind that the base of the truncated pyramid, thatis E, F, G, does not rest on. the bottom of the equilateral base triangle. Point D represents 100%.ethylene oxide. The base triangle represents the three other components and obviously 0% ethylene oxide. "For purpose of what is said herein, the'lower base of the truncated pyramid E, F, G, is a base parallel to the equilateral triangle but two units up, 'i. e., representing 2% of ethylene oxide. Similarly, the upper baseof the truncated pyramid HQI, J, lies in a plane which is' 39.5 unitsup'from the base, to wit, represents 39.5 ethylene oxide. Specifically, then, this invention is concerned withthe use ofcomponents in which the ethylene oxide component varies from 2% to 39.5% ethylene oxide. The problem then, presented is the determination of the other .three components,.to wit, butylene oxide, propylene oxide, and sucrose.

Actually, as far as the limiting pointsin the truncated pyramid are concerned, which has beenpreviously referred to in. Figure 1, it will'be noted that in the subsequent text there is a complete table giving thecomposition of these points for each successive range of ethylene oxide. In other words, a perfectly satisfactory repetition is available by means of these tables from a practical standpoint without necessarily resorting to the data of Figure 2.

Figure 2 shows a triangle and the three components other than ethylene oxide. These three components added together are less than 100%, to wit, 60.5% to 98%, but for reasons explained are calculated back..to 100%. This point is clarified subsequently by examination of the tables. It will be noted that Figure 2 shows a triangle 1, 4 and 6, which represents the bases (top, bottom, or for that matter, intermediate) of the truncated pyramid, also the area'in composition which is particularly pertinent to the present invention.

PART 2 As has been previously pointed out, the compositional limits of the herein described compounds are set by a truncated triangular pyramid which appears in Figure 1. It would be immaterial since the Figure A, B, C, D is a regular tetrahedron whether one considered A, B, C, as the base, 13, C, D, as the base, A, C, D, as the base, or A, B, D, as the base. In order to eliminate repetitious description which is obvious in light of the examples included we have selected A, B, C as the base. Another reason for so doing is that the preference 'is to'use ethylene oxide as the final component and this selection of A, B, C, as the base lends itself most readily to such presentation.

As has been suggested previously it is simplest to refer to Figure 2 and concern oneself with a 3-component system derived from sucrose, propylene oxide and butylene oxide. Such product can then be reacted with 2% to 39.5% of ethylene oxide based on the final composition so as to give the preferred examples of the instant invention.

Returning now momentarily to the preparation of the 3-component intermediate shown in Figure 2, it is obvious that hardly any directions are required to produce the compounds specified. However, referring to the composition of the initial reactants based on the triangle in the attached drawing, it will be noted that We have calculated the precentage of the three initial reactants for points 1 to 23, inclusive, so as to yield the intermediate derived from sucrose, propylene oxide, and butylene oxide. These pointsdetermine not only the triangle but also numerous points within the triangle. Furthermore, the points are selectedso the area is divided into five parts, three of-which are triangles'and twoof which are four- 6 sided figures. The triangles are defined by the points 1, '2 and 8; 2, 3 and'8; 5, 6 and 7; and the four-sided figures by the points 3, 4, 5 and 9 and finally 3, 8, '7 and 9.

Note that these data are included in Table .1 immediately following:

TABLE I Su- Propyl- Butyl- Su- Propyl- Su- Butyl- Points 'on crose, ene ene crose, ene crose, ene boundary peroxide, oxide, peroxide, peroxide, of area cent perpercent percent percent cent cent cent 1.- 0 I 86. '5 12. 5 1. 14 98. 86 7. 42 92. 58 1.0 63. 0 36.0 1. 56 98. 44 2. 70 97. 3 1.0 50.0 49. 0 1. 96 98.04 2. 0 98. 0 1.0 24. 0 75. O 4.0 I 96.0 1.32 98. 68 21.0 21. O 58.0 [50. 0 50. O 26. 55 73. 45 v 48. 5 17. 0 34. 5 74. 5 25. 5 58. 4 41. 6 36.0 36.0 23. 0 50.0 50. 0 56. 3 43.7 722. 5 55.0 22. 5 29.0 71.0 50.0 50.0 9 33. 0 33. 0 34. 0 50. 0 50. O 49. 2 50. 8 10 4. 0 27'. 5 68. 5 12. 7 87. 3 5. 52 94. 48 11 v 3. 5 38. 5 58. 5 8. 45 91. 55 5. 68 94. 32 2. 5 55. O 42. 5 4. 35 95. 65 5. 56 94. 4.4 2. 5 .59. 0 48. 5 4. 06 95. 94 4. 9 95. 1 3.0 68. 5 28. 5 4. 18 95. 82 9. 52 90.48 3 0 75.0 22. 0 3. 85 96. 15 12.0 88.0 2. 5 83. 0 14. 5 2. 92 97.08 14. 7 85. 3 7. 5 17.5 75. 0 '30. 0 70.0 9. 1 90.9 '14. 0 22. 5 63. 5 38. 3 61. 7 18.05 81. 95 24. 0 48. 5 27. 5 33. 1 66. 9 46. 6 53. 4 41. 5 .25. 5 33. 0 61. 8 38. 2 55. 7 44. 3 27. 5 51. 5 21. 0 34. 8 65. 2 56. 6 43. 4 21. 5 45. 5 33.0 32.0 68. 0 39. 4 60.6 17. 0 27. 0 56.0 38. 5 61. 4 23. 3 76. 7

Note the first column gives various points on the boundary of the triangle or within the triangle. Note thenext three columns represent the tertiary mixture corresponding to the initial reactants, i. e., the intermediate. These values represent percentages, by weight, of sucrose, butylene oxide and propylene oxide. Thus, it is apparent that one can select any particular point in Figure 2 and simply use the appropriate amount of oxide to obtain the selected intermediate. For instance, in regard to point I, all that-would be necessary would be to mix 86.5 pounds of propylene oxide with 12.5 pounds of butylene oxide and'use themixture to oxyalkylateone pound of sucrose.

Similarly, in Example 2, one need only mix 63 pounds of propylene oxide with 36 pounds of butylene oxide and use the mixture to oxyalkylate one pound of sucrose in a manner previously indicated.

Note that the fifth and sixth columns represent binary mixtures; for instance, in regard to the various points on the triangle and within the triangle we have calculated the initialmixture using sucrose and propylene oxide in the first. place and using sucrose and ethylene oxide inthe second place, which could be employed for subsequent oxyalkylation to give the particular composition required. Stated another way, we have calculated the composition for the sub-intermediates which, when reacted with the other oxide, propylene oxide or butylene oxide as the case may be, gives the intermediate, i. e., the three-component product.

Note that a binary intermediate for the preparation of point 1 can be prepared in any suitable manner involving 1.14 pounds of sucrose and 98.86 pounds of propylene oxide.

Referring now to the tertiary mixture table, it is apparent that for point 1 sucrose and propylene oxide together represent 87.5% and butylene oxide 12.5%. Therefore, one could employ 87.5 pounds of the binary mixture (21 sub-intermediate) and react it with 12 /2 pounds of butylene oxide to give the three-component product (the intermediate).

Similarly, in regard to the fifth and six columns, the mixture involved sucrose and propylene oxide. One could employ 1.56 pounds of sucrose and 98.44 pounds of propylene oxide. Such mixture need only. be reacted with butylene oxide in the proportion of 64.pounds of such mixture and 36 pounds of butylene oxide to give the 7 desired 3-component'product'. This is obvious data in regard to the tertiarymixtures'.

Referring now to columns 7 and 8, it is obvious one could produce an oxybutylated sucrose and then subject from the 8 means that the amount of ethylene oxide used as a reactant represents 2% to 39.5%of the final product with the proviso that.the remainder of the. product is represented by the three remaining components within the proit to reaction with propylene oxide. Using this procedure 5 portions set forth in Figure 2. in regard to point 1, it is obvious the mixture is obtained In prepar ng examples we have done nothing more exby 7.42 pounds of sucrose and 92.58 pounds of butylene cept 'use conventional oxyethylation, using an alkaline oxide. This product can th b bject d t tion catalyst such as powdered caustic soda or sodium methylwith propylene oxide in .the'ratio of 13.5 pounds of the ate; W have Operated at temperatures vary g from mixture and 86.5 pounds of propylene oxide. Similarly, 10 to 5 We have used oxyethylatlofl P in regard to point 2, it is obvious that one can react 2.70 sures 10 Pounds P square lnch p to 30 pounds P pounds of sucrose with 97.3 pounds of butylene oxide. q 1 3 not 15 p P Square 37 pounds of this mixture can then be reacted with 63 The'tlme P hijls Varled from 15 mlnutes hen pounds f propylene id I ust a small amount of oxide was employed, up to as much As previously pointed out the oxylkylafion of sucrose 15 3S 4 t 6 hours WIICII a larger amount Of O X1d e WES used. has been described in-the literature and is described Obviously the SPTIPIeSt 0f ealeulatlons Is Involved a also in detail above. All one needdo is ,employ such though We have E e data 111 tabular form conventional oxyalkylation procedure to obtain products Team that We e lndleafied that e P q eontalmng corresponding tothe compositions asxdefined. Attention ethylene OXlde qa i deslgnatfofl 4*; the one is again directed to the fact that one need not add the 20 havlng ethylene oxide carries the deslgnatlon B; the entire amount of either oxide at one time but that a P havmg 10% ethylene 15 c; the one havfng 15% small portion of one could be added and then another D; e P haVmg 20% 15 E; and the one having 25% small portion ofthe other, and the process repeated. 15 simllarlygdeslsnatwns G, H, I, J, and For purpose of illustration, we have prepared examples producfs'comalmng 2.715% to 395% of ethylene oxlde, three difierent ways corresponding to the compositions 25 P Q d as shown In Table of the socalled'intermediate in Figure .2, In the first TABLE III series, butylene oxide and ethylene oxide-"were mixed; this series is indicated as 1a, 2a, 3a, through andinclud- Proportions by weight ing 23a; in the second series, which represents our preferred procedure, butylene oxide Wasusedfirst, .followed Ex. N0. E h I 8c2 np0- Designaby propylene oxide. This series has been indicated as 1b, 25a? rii dia i gt non 2b, 3b, through and lncludmg 23b. Flnally, 1n the third gf series propylene oxide was used first, followed by butylene prece g oxide and the series identified as 1c, 2c, 30, through and 2 98 A including 230: 3 97 4 96 TABLE II 5 95 9 3% Composition Composition Composition 8 92 where oxides where butylwhere pro- 9 91 Composition correspondare mixed ene oxide is pylene oxide 10 90 ing to following point prior to used first 101- is used first 11 89 oxyalkylalowed by profollowed by 12 88 tion pylene oxide butylene 13 87 oxide 14 86 15 85 16 84 1e. 17 83 2c. 1s 82 3c. 19 81 4c. 20 80 5c. 21 79 6c. 22 78 7c. 23 77 8c. 24 76 9c. 25 75 F 100. 27.5 72.5 G 110. 30.0 70 H 120. 32.5 67.5 I 130. 35.0 65 J 140. 37.5 62.5 K 150. 39.5 00.5 L i?- Since it would be impossible to prepare all the variants which have been previously suggested, we have proceeded as follows: We have prepared examples corresponding 230: to the 23 points in Figure 2 by varying the amount of The products illustrated by the preceding examples are not, of course, the final products of the present invention. They represent intermediates. However, such intermediates require treatment with ethylene oxide to yield the product of the present invention.

PART 3 ethylene oxide from 2% to 39.5%. One example we have used 2%, another 5%, another 10%, another 15%, another 20% and another 25%, and on up to 39.5%, as shown. The intermediates used are those described in Table II, preceding. The prepared products have been described as follows: A-la, B-2b, C-3c, D-4a, etc. A-la is, of course, the product obtained by using 98% of intermediate la previously described in Table II, and 2%, by weight, of ethylene oxide; Example B-2b is obviously obtained by reacting 95%, by weight, of intermediate 2b with 5%, by weight, of ethylene oxide. Example 0-30 is obtained by reacting 90%, by weight, of intermediate 3c with'10%,by weight, of ethylene oxide. Example D-4a is obtained by reacting 85% of intermediate 4a with 15%,,by weight, ofv ethylene oxide. Example 13-51; is obtained'by reacting %ofintermediate 5b with 20% 9 by weight,.of ethylene oxide. Example F-6c is obtained by reacting 75% of intermediate 60 with 25% of ethylene oxide.

It will be noted that the last series of 7 examples in Table IV are connected with compositions corresponding to points 1, 5,10, 15, 16, and 23 in Figure 2. In these instances the compound having the F designation has 25% ethylene oxide; the one with a G designation has 27 /2%;

the 'one with the H designation, 30%; the one with the I designation, 32 /2-%; the one with the I designation, 35%; the one with the K designation, 37 /2 and the one with the Ld'esignation 39%%. Note that in one instance the table showsall three typesof preparation, that is inthe instance of 11621, J 16b, and 1160. The remaining examples 1n. Table IV, following, are self-explanatory.

TABLE IV Composition Composition Composition Where oxides where butylwhere pro- Co'mposition correspondare mixed ene oxide is pylene oxide ing, to following point prior to used first iolis used first: oxyalkylalowed by profollowed by 2 tion pylene oxide butylene oxide 1 A-lrz 1c. 2-- B-2b; 2c. 3. i 30. 0-30. 4.. 13-411 40 4c. 5--- n E5b 5c. 6-- 6a 6b F6c The same. procedures have been employed using other butylene oxides including mixtures having considerable isobutylene oxide and mixtures of the straight chain isomers with greater or lesser amount of the 2,3 isomer.

Where reference has been made in previous examples to the straight chain isomer, the product used was one which was roughly 85% or more of the 1,2 isomer and approximately, 15% of the 2,3-cisand the 2,3-transisomer'with substantially none or not over 1% of the isobutylene oxide.

In the preceding procedures one oxide has been added and then the other. One need not follow this procedure. The three oxides can be mixed together in suitable proportions. and subsequently subjected to joint oxyalkylatiOILSO as toobtain products coming within the specified limits. In such instances, of course, the oxyalkylation may be. described as random oxyalkylation insofar that one.cannot. determine the exact location of the butylene oxide, propylene oxide or ethylene oxide groups. In such instancesthe procedure again is identically the same as previously described, and, as a matter of fact, we have used such methods in connection with powdered sucrose.

If desired, one may add part of one oxide and then all the others and then return to the use of the first oxide. For example, one might use the procedure previously suggested, adding some butylene oxide, all the propylene oxide, all the ethylene oxide and then the remainder of the butylene oxide. Or, inversely, one may add some propylene oxide, then all the butylene oxide, then the remainder of the propylene oxide, and then the ethylene oxide. Or, any one of the threeoxide's could be added in portions so one oxide is added first, then the other two, then the first oxide is added again, then the other two. We have found no advantage in so doing; indeed, our preference has been to add all the butylene oxide first, then all the propylene oxide, and then the required amount of ethylene oxide.

As previously pointed-out, sucrose can be oxyethylated in the same way it' is oxybutylated, i. e., by powdering the sucrose, using a suitable catalyst, particularly an alkaline catalyst, and. adding the ethylene oxide. The changes previously mentioned are of 'diiference in degree only. In other words, oxyethylation will take place at a lower temperature, for'inst'an'ce, a top temperature of probably to-13.5: 6. instead of 145 to 150 C. The same weight of ethylene oxide could be added in 75% to 85% of the-time required for butylene oxide. The. pressure during-v-themeaction, instead of being 20 to 35-pounds:as inthe caseof butylene oxide, is apt to be 10, to pounds and at: timesa little higher, but frequently operates-at 15 pounds per-square inch or less. Otherwise, there is no difference: Note, however, that it is easier and preferable to oxyethyla-te last, i. e., have a liquid reaction productobtained by the use. of butylene oxide or propylene;oxide, =or. a combination ofthe two before the oxyethylation step..

Also, if'desired, the use of ethylene carbonate is a very convenient wayof oxyethylating sucrose. In fact, it can be oxyethylated. without the useof pressure.

Onecan.oxyalkylateusing an acid catalyst or an alkaline: catalyst or ataleasttinpart, without the use of any catalyst although such procedureis extremely slow'and uneconomicaL. In other: words, any' one of the conventionalcatalysts used: in -oxyalkylation may be employed. Itis. our. preference,.however,.to use an alkaline catalyst suchas. sodium methyl'ate, caustic soda, or the like.

Actually,v powdered sucrose may contain.l%, or somewhat. less, .of. water. to and subjected to vacuum, particularly when anhydrous nitrogen is passed through, the melted mas-s, the resultant. product appears to become substantially water free, Even. so, there may be a. few tenths of a percent and perhaps. only. a tracev of. water remaining in some instances.

The products. obtained by theabove. procedureusually show some color varying. from. alight amber to a pale straw. They can bebleached in theusual. fashion, using. bleachmg clays, charcoal, or an organic bleach, such as peroxide or peracetic acid, or the like.

Such products also have present a small amount of alkaline catalyst which can be removed by conventional means, or they can be neutralized by adding an equivalent amount of acid, such as hydrochloric acid. For many purposes the slight amount of'residual alkalinity is not objectionable.

There are certain variants which can be employedwithout detracting from the metes and bounds of the invention, butfor all practical purposes there is nothing to be gained bysuch variants and the result is merely increased cost. For instance, any one of the two oxides can-be replaced to a minor. percentage and usually to a very small degree, by oxide whichwould introduce substantially the same group a'longwith a side chain, for instance; one could" employ glycidyl methyl ether,

glycidyl ethyl ether, glycidyl isopropyl ether, glycidyl butyl ether or the like.

In the hereto appended claims reference has been made to glycolethers of" sucrose. Actually, it well may be that the products should be referred to as polyol ethers of sucrose in order to emphasize the fact that the final products of reaction have more than two hydroxyl radicals. However, the products may be considered as hypothetically derived by recation of sucrose with the glycols, such as ethylene glycol, butylene glycol, propylene glycol, or polyglycols. For this reason there seems to When such; powder isheated to that is, a position in which A, C, D, happen or B, C, D, or

A, B, D, happen to be the base instead of A, B, C. However, such further elaboration would add nothing to what has been said previously and is obviously omitted for purpose of brevity.

PART 4 As to the use of conventional demulsifying agent reference is made to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and effect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example J-16b, herein described.

Having thus described our invention, what we claim as new and desire to obtain by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to a demulsifying agent including a cogeneric mixture of a homologous series of glycol ethers of sucrose; said cogeneric mixture being derived exclusively from sucrose, butylene oxide, propylene oxide and ethylene oxide in such weight proportions, so that the average composition of said cogeneric mixture stated in terms of the initial reactants, lies approximately within the truncated triangular pyramid identified as E, H, F, I, G and J in Figure 1, with the proviso that the percentage of ethylene oxide is within the limits of 2% to 39.5%, by weight, and the remaining three initial reactants recalculated to 100% basis, lie approximately within the triangle defined in Figure 2 by points 1, 4 and 6.

2. The process of claim- 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst.

3. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added. first. I

4. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide is substantially free from isobutylene oxide.

5. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide consists of 85% or more of the 1,2-isomer and approximately 15% or less of the 2,3-isomeric form, and is substantially free from isobutylene oxide.

6. The process of claim 5 with the proviso that the reactant composition falls withinthe triangle defined by points 1, 2 and 8 in Figure 2.

7. The process of claim 5 with the proviso that the reactant composition falls within the triangle defined by points2, 3 and 8 in Figure 2.

8. The process of claim 5 with the proviso that the reactant composition falls within the four-sided figure defined by points 8, 3, 9 and 7.

9. The process of claim 5 with the proviso that the reactant composition falls within the four-sided figure defined by points 3, 4, 5 and 9.

10. The process of claim 5 with the proviso that the; reactant composition falls within the triangle'defined by I pointsS, 6 and 7.

, 1 1. A process for breaking-petroleum emulsions-of the water-in-oil type characterized by subjecting the emulsion to a demnlsifying agent including a cogeneric mixture of a homologous series of glycol ethers of sucrose; said cogeneric mixture being derived exclusively from sucrose, butylene oxide, propylene oxide and ethylene oxide in such weight proportions, so that the average composition of said cogeneric mixture stated in terms of the initial reactants, lies approximately within the truncated triangular pyramid identified as E, H, F, I, G and- .J in Figure 1, with the proviso that the percentage of ethylene axide is within the limits of 2% to 39.5%, by

weight, and the remaining three initial reactants recalculated to 100% basis, lie approximately within the triangle defined in Figure 2 by points 1, 4 and 6; with the proviso that the hydrophile properties of said cogeneric mixture in an equal weight of xylene, are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

12. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst.

13. The process of claim 11 with the proviso that oxy-.

alkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first.

14. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide is substantially' free from isobutylene oxide.

15. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide consists of or more of the 1,2-isomer and approximately 15% or T less of the 2,3-isomeric form, and is substantially free from isobutylene oxide.

16. The process of claim 15 with the proviso that the reactant composition falls within the triangle defined by points 1, 2 and 8 in Figure 2. V

17. The process of claim 15 with the proviso that the reactant composition falls within the triangle defined by points 2, 3 and 8 in Figure 2.

18. The process of claim 15 with the proviso that the reactant composition falls within the four-sided figure defined by points 8, 3, 9 and 7.

19. The process of claim 15 with the proviso that the reactant composition falls within the four-sided figure defined by points 3, 4, 5 and 9.

20. The process of claim 15 with the proviso that the reactant composition falls within the triangle defined by points 5, 6 and 7.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO A DEMULSIFYING AGENT INCLUDING A COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF SUCROSE; SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM SUCROSE, BUTYLENE OXIDE, PROPYLENE OXIDE AND ETHYLENE OXIDE IN SUCH WEIGHT PROPORTIONS, SO THAT THE AVERAGE COMPOSITION OF SAID COGENERIC MIXTURE STATED IN TERMS OF THE INITIAL REACTANTS, LIES APPROXIMATELY WITHIN THE TRUNCATED TRIANGULAR PYRAMID IDENTIFIED AS E, H, F, I, G AND J IN FIGURE 1, WITH THE PROVISO THAT THE PERCENTAGE OF ETHYLENE OXIDE IS WITHIN THE LIMITS OF 2% TO 39.5%, BY WEIGHT, AND THE REMAINING THREE INITIAL REACTANTS RECALCULATED TO 100% BASIS, LIE APPROXIMATELY WITHING THE TRIANGLE DEFINED IN FIGURE 2 BY POINTS 1, 4 AND
 6. 